錯体分子集積による複合アニオン型極性物質群の合成と機能創発

• Project Area: Synthesis of Mixed Anion Compounds toward Novel Functionalities
• Project/Area Number: 19H04701
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Kyushu University
• Principal Investigator: 大谷 亮 九州大学, 理学研究院, 准教授 (30733729)
• Project Period (FY): 2019-04-01 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000); Fiscal Year 2020: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000); Fiscal Year 2019: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
• Keywords: 金属錯体 / プロトン伝導 / 配位高分子 / 分子集積

Outline of Research at the Start

歪んだ四角錐形構造を持つ極性金属錯体分子を最小単位として異方的に集積させることで、複合アニオン型一次元金属窒化物を合成し機能開拓を行う。組成、集積構造、電気・磁気機能の相関について系統的かつ総合的に解釈することで、極性錯体分子の異方的集積という錯体化学的手法と固体化学的手法を組み合わせることでしか得られない“一次元金属窒化物の機能化学”を展開する。

Outline of Annual Research Achievements

本年度は、ナイトライドアニオン(N3-)、シアノアニオン(CN-)から成る五配位構造の極性錯体分子 [MnN(CN)4]2- を最小単位として、室温で分子集積することで得られる極性一次元物質K2MnN(CN)4.H2Oの単結晶および粉末を用いたプロトン伝導性の評価を行った。温度依存および湿度依存の交流インピーダンス測定から一次元鎖間に取り込まれた結晶水由来のプロトン伝導を示すことが明らかになった。湿度上昇に伴いプロトン伝導度の上昇が観測され、これは、粉末試料の水吸着測定の結果からも結晶水の増加によるものであることが分かった。特に、湿度80%において室温で10-2オーダーの伝導度を示し、スーパープロトン伝導体として機能することが分かった。プロトン伝導の活性化エネルギーを算出したところ、水分子の移動を伴うプロトン伝導メカニズムが支持されたが、構造との相関に関して更に検討が必要であると考えている。
更に、単結晶試料を用いて直流バイアス電圧をかけた状態で、交流インピーダンス測定を行うことで、極性構造に基づくプロトン伝導能の能動制御について検討した。バイアス電圧の方向により、プロトン伝導度が顕著に変化することが分かり、すなわち、プロトンの流れやすい方向と流れにくい方向があることが示唆された。これは、非常に珍しいプロトン整流性をもつ固体物質であることを示唆している。一方で、これまでのところ、極性構造のどちらの方向にバイアスを印加しているかは明らかとなっておらず、計算などを用いた検討が今後さらに必要である。

Research Progress Status

令和2年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和2年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] シドニー大学(オーストラリア)
• [Journal Article] Coordination Geometry Changes in Amorphous Cyanide-Bridged Metal Organic Frameworks upon Water Adsorption (2021)
  • Author(s): Yoshino Haruka、Yamagami Kohei、Wadati Hiroki、Yamagishi Hirona、Setoyama Hiroyuki、Shimoda Sayuri、Mishima Akio、Le Ouay Benjamin、Ohtani Ryo、Ohba Masaaki
  • Journal Title: Inorganic Chemistry Volume: 60 Issue: 5 Pages: 3338-3344
  • DOI: 10.1021/acs.inorgchem.0c03742
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Theoretical investigation of tetrahedral distortion of four-coordinate iron(ii) centres in FePd(CN)4 (2021)
  • Author(s): Fujii Susumu、Ohtani Ryo、Kuwabara Akihide
  • Journal Title: Dalton Transactions Volume: 50 Issue: 6 Pages: 1990-1994
  • DOI: 10.1039/d0dt04155f
  • Peer Reviewed
• [Journal Article] Light-induced excited spin state trapping in iron(iii) complexes (2021)
  • Author(s): Nakaya Manabu、Ohtani Ryo、Lindoy Leonard F.、Hayami Shinya
  • Journal Title: Inorganic Chemistry Frontiers Volume: 8 Issue: 2 Pages: 484-498
  • DOI: 10.1039/d0qi01188f
  • Peer Reviewed
• [Journal Article] Responsive Four‐Coordinate Iron(II) Nodes in FePd(CN) 4 (2020)
  • Author(s): Ohtani Ryo、Matsunari Hiromu、Yamamoto Takafumi、Kimoto Koji、Isobe Masaaki、Fujii Kotaro、Yashima Masatomo、Fujii Susumu、Kuwabara Akihide、Hijikata Yuh、Noro Shin‐ichiro、Ohba Masaaki、Kageyama Hiroshi、Hayami Shinya
  • Journal Title: Angewandte Chemie International Edition Volume: 59 Issue: 43 Pages: 19254-19259
  • DOI: 10.1002/anie.202008187
  • Peer Reviewed / Open Access
• [Journal Article] Pseudo‐Membrane Jackets: Two‐Dimensional Coordination Polymers Achieving Visible Phase Separation in Cell Membrane (2020)
  • Author(s): Ohtani Ryo、Kawano Kenichi、Kinoshita Masanao、Yanaka Saeko、Watanabe Hikaru、Hirai Kenji、Futaki Shiroh、Matsumori Nobuaki、Uji‐i Hiroshi、Ohba Masaaki、Kato Koichi、Hayami Shinya
  • Journal Title: Angewandte Chemie International Edition Volume: 59 Issue: 41 Pages: 17931-17937
  • DOI: 10.1002/anie.202006600
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Luminescent ionic liquid formed from a melted rhenium(V) cluster (2020)
  • Author(s): J. Yanagisawa, T. Hiraoka, F. Kobayashi, D. Saito, M. Yoshida, M. Kato, F. Takeiri, G. Kobayashi, M. Ohba, L. F. Lindoy, R. Ohtani, S. Hayami
  • Journal Title: Chem. Commun. Volume: 56 Issue: 57 Pages: 7957-7960
  • DOI: 10.1039/d0cc02937h
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Vapor Switching of the Luminescence Mechanism in a Re(v) Complex (2020)
  • Author(s): Kenta Sasaki, Hitomi Yamate, Haruka Yoshino, Hiroki Miura, Yuushi Shimoda, Kiyoshi Miyata, Ken Onda, Ryo Ohtani, Masaaki Ohba
  • Journal Title: Chem. Commun. Volume: 56 Issue: 85 Pages: 12961-12964
  • DOI: 10.1039/d0cc05462c
  • Peer Reviewed
• [Journal Article] Double-layered honeycomb architectures constructed via hierarchical self-assembly of hexagonal spin crossover cobalt(ii) metallacycles (2020)
  • Author(s): Akiyoshi Ryohei、Kuroiwa Keita、Sakuragi Mina、Yoshimoto Soichiro、Ohtani Ryo、Nakamura Masaaki、Lindoy Leonard F.、Hayami Shinya
  • Journal Title: Chemical Communications Volume: 56 Issue: 43 Pages: 5835-5838
  • DOI: 10.1039/d0cc02628j
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Swift and Efficient Nuclear Spin Conversion of Molecular Hydrogen Confined in Prussian Blue Analogs (2020)
  • Author(s): Yuta Ohtsubo, Akio Mishima, Akihiro Hori, Ryotaro Matsuda, Ryo Ohtani, Masaaki Ohba
  • Journal Title: Chem. Lett. Volume: 49 Issue: 2 Pages: 149-152
  • DOI: 10.1246/cl.190829
  • NAID: 130007795207
  • Peer Reviewed / Open Access
• [Journal Article] Guest Modulated Spin States of Metal Complex Assemblies (2020)
  • Author(s): Nakaya Manabu、Ohtani Ryo、Hayami Shinya
  • Journal Title: European Journal of Inorganic Chemistry Volume: 2020 Issue: 39 Pages: 3709-3719
  • DOI: 10.1002/ejic.202000553
  • Peer Reviewed
• [Journal Article] Homo- and Heterosolvent Modifications of Hofmann-Type Flexible Two-Dimensional Layers for Colossal Interlayer Thermal Expansions (2019)
  • Author(s): Ohtani Ryo、Yanagisawa Junichi、Matsunari Hiromu、Ohba Masaaki、Lindoy Leonard F.、Hayami Shinya
  • Journal Title: Inorganic Chemistry Volume: 58 Issue: 19 Pages: 12739-12747
  • DOI: 10.1021/acs.inorgchem.9b01660
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Slow Magnetic Relaxation Triggered by a Structural Phase Transition in Long-Chain-Alkylated Cobalt(II) Single-Ion Magnets (2019)
  • Author(s): Kobayashi Fumiya、Ohtani Ryo、Nakamura Masaaki、Lindoy Leonard F.、Hayami Shinya
  • Journal Title: Inorganic Chemistry Volume: 58 Issue: 11 Pages: 7409-7415
  • DOI: 10.1021/acs.inorgchem.9b00543
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Water‐Induced Breaking of the Coulombic Ordering in a?Room‐Temperature Ionic Liquid Metal Complex (2019)
  • Author(s): Hiraoka Tomoaki、Ohtani Ryo、Nakamura Masaaki、Lindoy Leonard F.、Hayami Shinya
  • Journal Title: Chemistry - A European Journal Volume: 25 Issue: 31 Pages: 7521-7525
  • DOI: 10.1002/chem.201900069
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Weak ferromagnetism derived from spin canting in an amido-bridged homochiral Mn(iii) 1-D coordination polymer (2019)
  • Author(s): Kusumoto Sotaro、Koga Atsushi、Kobayashi Fumiya、Ohtani Ryo、Kim Yang、Lindoy Leonard F.、Hayami Shinya、Nakamura Masaaki
  • Journal Title: Dalton Transactions Volume: 48 Issue: 24 Pages: 8617-8622
  • DOI: 10.1039/c9dt00593e
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Phosphorescence at Low Temperature by External Heavy‐Atom Effect in Zinc(II) Clusters (2019)
  • Author(s): Kobayashi Fumiya、Ohtani Ryo、Teraoka Saki、Yoshida Masaki、Kato Masako、Zhang Yingjie、Lindoy Leonard F.、Hayami Shinya、Nakamura Masaaki
  • Journal Title: Chemistry - A European Journal Volume: 25 Issue: 23 Pages: 5875-5879
  • DOI: 10.1002/chem.201900343
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Consecutive oxidative additions of iodine on undulating 2D coordination polymers: Formation of I-Pt-I chains and inhomogeneous layers (2019)
  • Author(s): Ryo Ohtani, Riho Yamamoto, Hiroyoshi Ohtsu, Masaki Kawano, Jenny Pirillo, Yuh Hijikata, Masaaki Sadakiyo, Leonard F. Lindoye, and Shinya Hayami
  • Journal Title: Dalton Transactions Volume: 印刷中 Issue: 21 Pages: 7198-7202
  • DOI: 10.1039/c8dt04624g
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Presentation] Melting of a 1D cyanide-bridged coordination polymer (2019)
  • Author(s): Ryo Ohtani
  • Organizer: 7th Asian Conference on Coordination Chemistry (ACCC7) (Kuala Lumpur, Malaysia)
  • Int'l Joint Research
• [Presentation] Ionic liquid metal complexes consisting of tetracyano-metalate units (2019)
  • Author(s): Ryo Ohtani
  • Organizer: 第69回錯体化学討論会（名古屋大学・名古屋）
• [Presentation] Control of structural distortions for polar materials (2019)
  • Author(s): Ryo Ohtani
  • Organizer: the Symposium of Functional Coordination Chemistry 2019 (Sun Yet-Sen university, Guangzhou, China)
  • Int'l Joint Research / Invited
• [Remarks]
  • URL: https://sites.google.com/view/ryoohtani-chem/home
• [Remarks]
  • URL: https://hyoka.ofc.kyushu-u.ac.jp/search/details/K007155/index.html